JPH01268667A - Production of surfactant - Google Patents

Abstract

PURPOSE:To obtain the title compound useful as a surfactant simply, efficiently at low cost and in high yield, by reacting an imidazoline or amidoamine with a monohalogenated acetic acid or a salt thereof by using a specific polar solvent. CONSTITUTION:In producing an amino acid type surfactant shown by formula IV (M is alkali metal, ammonium, etc.) or formula V by reacting an imidazoline shown by formula I (R is 7-23C alkyl, hydroxyalkyl, aralkyl, etc.) or an amidoamine shown by formula II or formula III with a monohalogenated acetic acid or a salt thereof, >=3.0wt.% based on total amounts of raw material compounds feds of one or more polar solvents selected from 1,3-butanediol, 1,4-butanediol, propylene glycol, ethylene glycol, ethanol, isopropyl alcohol and diethylene glycol is used.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to amide amino acid type activators, specifically, salts of N-acyl-No-hydroxyethyl-No-carboxymethylethylenediamine, N-acyl-N −
<2-Hydroxyethyl)-N', N'-Bis(carboxymethyl)ethylenediamine salts, or a mixture thereof.

[Problems to be solved by conventional techniques and inventions] In recent years,
With increasing demands for safety and low irritation, surfactants that cause mild irritation to the skin, eyes, etc. are becoming preferred. One of the surfactants that meet these demands is an imidacillin surfactant.

The imidacillin surfactant is produced by a method of reacting alkylimidacillin with monochloroacetic acid or an alkali metal salt thereof to make it amphoteric. The imidacillin surfactants obtained by this reaction have long been thought to have an imidacillin skeleton, but recent research has revealed that imidacillin has a ring-opened structure, such as the general formula (TV) or (V). It has been revealed that the structure is as shown in the figure.

CHCH2C0 4 In formula (IV) and formula (V), R and M are the same as defined above) Even today, such surfactants are called imidacillin surfactants due to old custom, but the present specification In this book, it is called an ``amide amino acid type activator'' because of this structure. Therefore, this amide amino acid type activator can be produced by reacting alkylimidacillin or its hydrolyzate, amide amine, with monochloroacetic acid or an alkali metal salt thereof in the presence of an alkali.

A method for producing an amide amino acid type surfactant mainly containing the structure (TV>) is described in U.S. Pat. No. 2.961.451. The production method involves adding a small amount of diluted hydrochloric acid to the secondary amide type amine compound represented by the general formula (n), and then adding monochloroacetic acid at 1°25° C. while maintaining the temperature at 67 to 73° C. After neutralizing the reaction mixture with monochloroacetic acid and approximately the same mole of alkali at 50°C or lower, the reaction temperature was raised to around 70°C, and approximately the same mole of alkali was further added over 1 hour. , and then maintained at around M70° C. for several hours to obtain an amide amino acid type surfactant mainly containing the general formula (IV).

A method for producing an imidacillin surfactant mainly having the structure of formula (V) is described in U.S. Pat. An aqueous solution of sodium monochloroacetate was prepared by dropping 2.2 times the mole of alkali, and after raising the reaction temperature to around 100°C, 1 mole of imidacillin was added dropwise, and then the temperature was maintained at around 100°C to prepare the above-mentioned solution. A method for obtaining an amide amino acid type surfactant mainly containing general formula (V) is disclosed.

The present inventors carried out a follow-up test based on the above patent, investigated the amount of unreacted amidoamine contained in the surfactant after the reaction was completed using high performance liquid chromatography, and determined the conversion rate with respect to the raw material amine. However, U.S. Patent No. 2.71
The method of No. 3.068 has a conversion rate of 88% and is similar to that of U.S. Patent No. 2.068.
No. 961.451 had a conversion rate of 90.5%. That is, in these methods, hydrolysis of monochlorosodium acetate tends to occur, and as a result, unreacted amidoamine or imidacillin remains, resulting in a decrease in yield.

There is also a known method for improving the above drawbacks by using a large amount of monochloroacetic acid or its salt, but in this case, a large amount of common salt and sodium glycolate, which is a hydrolyzate, is produced as a by-product. , resulting in impaired product stability in shampoo systems.

[Means to solve problems]

The present inventors have overcome the above-mentioned conventional drawbacks, and by using a suitable amount of monohalogenated acetic acid or its salt with less unreacted amidoamine or imidacilline, the present inventors have achieved low cost and reduced the content of sodium glycolate and salt as by-products. As a result of extensive research in order to develop a method for efficiently producing high-quality amido-amino acid type activators with a small amount of discovered that the reaction was dramatically accelerated by adding a specific polar solvent,
The present invention has now been completed.

That is, the present invention provides imidacillin CH, CH2DH represented by the general formula (I) (in the formula (I), R represents an alkyl group having 7 to 23 carbon atoms, a hydroxyalkyl group, an aralkyl group, or an alkenyl group), or a general An amidoamine represented by formula (II) or (III) (formula (n), in (I), R is the same as formula (I)) is reacted with monohalogenated acetic acid or a salt thereof to obtain the general formula (T
When producing an amide amino acid type surfactant represented by V) or (V), CH2C00M CHCH2C0 1 formula (rV), in (V), R is the same as in formula (1), and the targeted alkali metal atom, ammonium or a cationic group of alkanolamine) 1. One or more polar solvents selected from the group consisting of 1,3-butanediol, 1,4-butanediol, propylene glycol, ethylene glycol, ethanol, isopropyl alcohol, and diethylene glycol. , a method for producing an amidoamino acid type surfactant, characterized in that 3.0% by weight or more of imidacillin or amidoamine and monohalogenated acetic acid or its salt is added to the total charge amount.

The present invention will be explained in more detail below.

Examples of the monohalogenated acetic acid or a salt thereof used in the present invention include monochloroacetic acid or a salt thereof, monobromoacetic acid or a salt thereof, and the like.

The raw material amines include 1-hydroxyethyl-2-heptylimidacillin, 1-hydroxyethyl-2-undecylimidacilline, 1-hydroxyethyl-2-cocoyl imitasoline, 1-hydroxyethyl-2- Heptadecyl imidacillin, N-lauroyl-No-hydroxyethylethylenediamine, N-stearoyl-N.

-Hydroxyethylethylenediamine and the like.

Examples of polar solvents include ethanol, isopropyl alcohol, 1,3-butanediol, 1,4-butanediol, propylene glycol, ethylene glycol, and diethylene glycol.

To specifically explain the method of reacting these monohalogenated acetic acids or their salts with alkylimidacillin or amidoamine, the amide amino acid type activity mainly having a secondary amide type structure represented by the above general formula (IV). When manufacturing the agent, first, imidacillin is diluted with an alkaline aqueous solution to 80-80%
Ring opening is performed at 90°C to give amidoamine. 1 mole of this raw material amidoamine and 1 to 2 times the mole, preferably 1.1 to 1
．． Five times the mole of monohalogenated acetic acid or its salt is reacted in an aqueous solution at 50 to 100°C, preferably 60 to 80°C, with stirring, and at this time, a polar solvent such as ethanol is mixed with the raw amidoamine and monohalogenated acetic acid or a salt thereof. Add 3% by weight or more of the salt to the total amount charged, and then add dropwise an alkali to keep the pH of the reaction solution in the range of 8 to 9, or raw amidoamine and monohalogenated acetic acid or its salt. After adding polar solvent and alkali together, 5
The reaction is carried out at 0 to 100°C, preferably 60 to 80°C, with stirring. If the reaction temperature is below 40° C., the raw amidoamine will be difficult to dissolve, and the reaction rate of the raw amidoamine to an amphoteric product will also be slow. Moreover, if the temperature is 100° C. or higher, the amphoteric activator will become more discolored and decomposed, which is not preferable.

Examples of the alkali include caustic potash, caustic soda, soda carbonate, potassium carbonate, and bicarbonate of soda.

In addition, when producing an amide amino acid type activator mainly having a tertiary amide type structure represented by the above general formula (V), first, for 1 mole of imidacillin or amido amine represented by the above general formula (III), 2 to 3 times the mole, preferably 2
．． After charging an aqueous solution of 0 to 2.5 times the mole of monohalogenated acetic acid or its salt, the temperature is 50 to 100°C, preferably 60°C.
Imidacillin or the amidoamine 1 represented by the general formula (III) is heated in a temperature range of ~80°C and stirred.
At this time, a polar solvent such as isopropyl alcohol is added in an amount of 3% by weight or more based on the total amount of raw material imidacillin and monohalogenated acetic acid or its salt, and then the pH of the reaction solution is adjusted to 8 to 9. Drop the alkali to keep it within the range. If the reaction temperature is below 40°C, the rate of reaction of imidacillin or amidoamine to the amphoteric compound will be slow, and if it is above 100°C, the coloring and decomposition of the amphoteric activator will become severe, which is not preferable.

The present inventors used high performance liquid chromatography to
When the remaining amount of unreacted amidoamine was tracked over time during the reaction, it was found that the reaction rate in the reaction system in which a polar solvent was added was extremely faster than in the system in which no polar solvent was added, and that the content of unreacted amidoamine in the reaction product was extremely high. It was discovered that only traces existed.

The amount of polar solvent added in the present invention may be 3.0% by weight or more based on the total amount charged.

Although there is no particular upper limit, the effect of adding a polar solvent on the conversion rate is that when a certain amount is exceeded, the conversion rate reaches an equilibrium and there is no point in adding any more polar solvent. The active agent obtained in the present invention can be used in shampoo compositions, etc., as long as it does not inhibit the functions thereof. It is preferable that the amount of polar solvent in the resulting surfactant composition is 10% by weight or less.

The polar solvents used in the present invention may be used alone or in combination.

〔Effect of the invention〕

As described above, according to the method of the present invention, an amidoamic acid type surfactant can be produced extremely easily and efficiently at a high reaction rate without increasing the molar ratio of monohalogenated acetic acid or its salt. Moreover, the operation is extremely simple, and from this point of view as well, it is suitable for easy industrial implementation.

The amidoamino acid type surfactant obtained by the method of the present invention has a small content of unreacted amidoamine, and according to the method of the present invention, the target substance can be obtained in high yield. In addition, since the reaction is carried out efficiently, the amount of monohalogenated acetic acid or its salt used is reduced, resulting in lower cost and lower content of sodium glycolate and salt as by-products, resulting in product stability in shampoo systems. Sexuality is also improved.

〔Example〕

Next, the present invention will be explained based on Examples, but the scope of the present invention is not limited by these. In the examples, % is by weight unless otherwise specified.

Example 1 268 g (1 mol) of 1-hydroxyethyl-2-undecylimidacillin, 90 g of water, and 2 g of sodium hydroxide were placed in a 4-tubular flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer, and the mixture was stirred. The mixture was heated to 80° C. and stirred at that temperature for about 2 hours, followed by ring opening of imidacillin.

Next, 140 g of separately prepared sodium monochloroacetate (1
, 2 mol) and 539 g of water, and then 61 g of ethanol was added to the container. Next, increase the temperature of the solution to 70~
120g of 40% sodium hydroxide while keeping at 80℃
was added dropwise over 3 hours. After finishing dropping, add another 75 to 80
Aging was carried out at a temperature of °C. During this period, unreacted amidoamine was measured using high performance liquid chromatography, and the unreacted amidoamine content in the reaction mixture was found to be 0.2 after 4 hours.
%, and cooled. The conversion rate with respect to the raw material imidacillin was 99.2%. When the reaction product was analyzed using high performance liquid chromatography, it was confirmed that it was an approximately 30% aqueous solution mainly containing N-lauroyl-No-hydroxyethyl-No-sodium carboxymethylethylenediamine.

As a result of preparing and evaluating a cleaning agent using the obtained aqueous solution,
It had excellent detergency and foaming power, and was hypoallergenic to the skin.

Example 2 The same procedure as Example 1 was carried out except that the amount of ethanol added was changed, and the results of examining the relationship with the conversion rate of the raw material imidacillin are shown in Table 1 together with the results of Example 1.

Table 1 * The amount of ethanol added is the weight percent of the total amount of raw material imidacillin and sodium monochloroacetate. The amount of ethanol added is the amount relative to the amount of synthetic material imidacillin and sodium monochloroacetate. Also, N-lauroyl-N'-hydroxyethyl in the reaction product =
The amount of water was adjusted so that the N'-sodium carboxymethylethylenediamine content was 30%. As is clear from Table 1, the conversion rate of raw material imidacillin in the reaction system to which ethanol was added was good, and Comparative Example 1 (additive-free system)
There is a clear difference compared to

Comparative Example 1 268 g (1 mol) of 1-hydroxyethyl-2-undecylimidacillin, 90 g of water, and hydroxide were placed in a 4-ton flask equipped with a stirrer, condenser, dropping funnel, and thermometer.
Add 2g of IJum and heat to 80℃ while stirring.
After stirring at the same temperature for about 2 hours, imidacillin was ring-opened.

Next, 139.8 g of separately prepared sodium monochloroacetate
(A solution of 1,2 morph and 602 g of water was placed in a container.

Next, 120 g of 40% sodium hydroxide was added dropwise over 3 hours while maintaining the temperature of the solution at 70 to 80°C.

After completion of the dropwise addition, further ripening was carried out at a temperature of 75 to 80°C, during which unreacted amidoamine was measured using high performance liquid chromatography, and the unreacted amidoamine content in the reaction mixture was 3.20% 0 in 4 hours. %, and cooled down. The conversion rate with respect to the raw material imidacillin is 86.
It was 3%.

Example 3 Into the reactor of Example 1, 268 g (1 mole) of 1-hydroxyethyl-2-undecylimidacilline, 90 g of water, and 2 g of IJium hydroxide were added, and while stirring, the reaction mixture was heated to 80 g.
The mixture was heated to .degree. C. and stirred at that temperature for about 2 hours, followed by opening of imidacillin.

Next, 151.5 g of separately prepared sodium monochloroacetate
A solution of (1.3 mol) and 470 g of water was charged, and then 122 g of 1,3-butanediol was added. Next, 130 g of 40% sodium hydroxide was added dropwise over 3 hours while maintaining the temperature of the solution at 70 to 80°C. After Dripping Forest 7,
Further aging was carried out at a temperature of 75 to 80°C, during which unreacted amidoamine was measured using high performance liquid chromatography, and the unreacted amidoamine content in the reaction mixture was determined to be 4.
After confirming that the concentration had decreased to 0.2% over time, it was cooled. The conversion rate with respect to the raw material imidacillin was 99.2%.

When the reaction product was analyzed using high performance liquid chromatography, it was confirmed that it was an approximately 30% aqueous solution mainly containing N-lauroyl-No-hydroxyethyl-No-sodium carboxymethylethylenediamine.

Example 4 Into the reactor of Example 1, 233 g of sodium monochloroacetate (
2 mol) and 562 g of water were heated to 50°C with stirring, and then 286 g (1 mol) of N-lauroyl-N-hydroxyethylethylenediamine, which had been synthesized separately, was added while maintaining the temperature at 50 to 60°C. I prepared it. After the preparation is complete, add 100g of ethanol, raise the temperature to 70'C, and while maintaining this temperature add 200g of 40% NaOH.
was added dropwise over 3 hours.

After completion of the dropwise addition, aging was further carried out at a temperature of 70°C for 2 hours, during which unreacted amidoamine was measured using high performance liquid chromatography, and the unreacted amidoamine content in the reaction mixture was reduced to 0.4% in 4 hours. After confirming that the temperature had decreased, the temperature was cooled. Conversion rate to raw amidoamine is 98.1
%Met.

When the reaction product was analyzed using high performance liquid chromatography, it was found to be an approximately 30% aqueous solution mainly containing N-lauroyl-N-(2-hydroxyethyl)-N',N'-bis(sodium carboxymethyl)ethylenediamine. #1 magazine for being

Example 5 Into the reactor of Example 1, 233 g of sodium monochloroacetate (
2 mol) and 580 g of water were heated to 50°C while stirring, and then 268 g of 1-hydroxyethyl-2-undecylimidacilline was added while maintaining the temperature at 50 to 60°C.
(1 mol) was added dropwise over 1 hour. After the dropwise addition, 100g of ethanol was added, the temperature was raised to 70°C, and while maintaining this temperature, 200g of 40% NaOH was added dropwise over 3 hours. After completion of the dropwise addition, aging was further carried out at a temperature of 70°C for 2 hours, during which unreacted amidoamine was measured using high performance liquid chromatography, and the unreacted amidoamine content in the reaction mixture was reduced to 0.5% in 4 hours. After confirming that the temperature had decreased, the temperature was cooled. The conversion rate with respect to the raw material imidacillin was 97.6%. The reaction product was analyzed using high performance liquid chromatography and was found to be N-lauroyl-
It was confirmed that it was an approximately 30% aqueous solution mainly containing N-(2-hydroxyethyl')-N', N'-bis(sodium carboxymethyl)ethylenediamine.

Comparative Example 2 Into the reactor of Example 1, 233 g of sodium monochloroacetate (
2 mol) and 662 g of water were heated to 50°C while stirring, and then 286 g (1 mol) of N-lauroyl-N-hydroxyethylethylenediamine, which had been separately synthesized and wiped while maintaining the temperature at 50 to 60°C, was added. I prepared it. After the preparation was completed, the temperature was raised to 70° C., and while maintaining this temperature, 200 g of 40% NaOH was added dropwise over 3 hours. After completion of the dropwise addition, aging was further carried out at a temperature of 70°C for 2 hours, during which time unreacted amidoamine was measured using high performance liquid chromatography, and it was found that the unreacted amidoamine content in the reaction mixture had decreased to 1.9%. was confirmed and cooled. The conversion rate with respect to the raw material imidacillin was 90.2%.

Comparative Example 3 Into the reactor of Example 1, 233 g of sodium monochloroacetate (
2 mol) and 680 g of water were heated to 50°C while stirring, and then 268 g of 1-hydroxyethyl-2-undecylimidacilline was added while maintaining the temperature at 50 to 60°C.
(1 mol) was added dropwise over 1 hour. After dropping, the temperature was raised to 70°C, and while maintaining this temperature, 40% Na
200 g of OH was added dropwise over 3 hours. After dropping, add 7 more
Aging was performed at a temperature of 0°C for 2 hours, during which time unreacted amidoamine was measured using high performance liquid chromatography, and the unreacted amidoamine content in the reaction mixture was 2.1%.
After confirming that the temperature had dropped to this level, the temperature was cooled. The conversion rate with respect to the raw material imidacillin was 89.9%.

Applicant's agent - Kaoru Furutani

Claims (1)

[Claims] 1. Imidazoline represented by general formula (I) ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ (I) (In formula (I), R represents an alkyl group, hydroxyalkyl group, aralkyl group, or alkenyl group having 7 to 23 carbon atoms) Or, general formula (II) or (III) ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In formulas (II) and (III), R is the same as formula (I) ) and monohalogenated acetic acid or its salt to produce an amide amino acid type surfactant represented by the general formula (IV) or (V), there are ▲mathematical formulas, chemical formulas, tables, etc.▼(IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In formulas (IV) and (V), R is the same as in formula (I), and M is an alkali metal atom, ammonium, or an alkanolamine cationic group. 1,3-butanediol, 1,4-butanediol, propylene glycol, ethylene glycol, ethanol, isopropyl alcohol and diethylene glycol, imidazoline or amidoamine and monohalogenated acetic acid. A method for producing an amide amino acid type surfactant, characterized in that 3.0% by weight or more is added to the total amount of the amide amino acid type surfactant or its salt.